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ConspectusThe redox reaction pathway is crucial to the sustainable production of the fuels and chemicals required for a carbon-neutral society. Our society is becoming increasingly dependent on devices using batteries and electrolyzers, all of which rely on a series of redox reactions. The overall properties of oxide materials make them very well suited for such electrochemical and catalytic applications due to their associated cationic redox properties and the static site-adsorbate interactions. As these technologies have matured, it has become apparent that defect-driven redox reactions, defect-coupled diffusion, and structural transformations that are both time- and rate-dependent are also critical materials processes. This change in focus, considering not only redox properties but also more complex, dynamic behaviors, represents a new research frontier in the molecular sciences as they are strongly linked to device operation and degradation and lie at the heart of various phenomena that take place at electrochemical interfaces. Fundamental studies of the structural, electronic, and chemical transformation mechanisms are key to the advancement of materials and technological innovations that could be implemented in various electrochemical systems.In this Account, we focus on recent studies and advances in characterizing and understanding the dynamic redox evolution and structural transformations that take place in model perovskites and layered oxides under reactive conditions and correlate them with degradation mechanisms and operations in electrolyzers and batteries. We show that the dynamic evolution of oxygen vacancies and cationic migration in the surface or bulk occurs at the solid-liquid interface, using a combination of different synchrotron-based X-ray spectroscopies and scattering probes. Detailed redox-structure-reactivity correlation studies show how defects and diffusion processes can be tailored to drive various physical and chemical transformations in electrolyzers and batteries. We also highlight a strong correlation between oxygen redox reactivity and structural reorganization in both model thin films and particles, helping to bridge the gap between fundamental studies of the reaction mechanism and device applications. On the basis of these findings, we discuss strategies to probe and tune the redox reactivity and structural stability of the redox-active oxide interphase toward devising efficient pathways for energy and chemical harvesting.

P2-structured Na0.67Ni0.33Mn0.67O2 (PNNMO) is a promising Na-ion battery cathode material, but its rapid capacity decay during cycling remains a hurdle. Li doping in layered transition-metal oxide (TMO) cathode materials is known to enhance their electrochemical properties. Nevertheless, the influence of Li at different locations in the structure has not been investigated. Here, the crystallographic role and electrochemical impact of lithium on different sites in PNNMO is investigated in Li x Na0.67-y Ni0.33Mn0.67O2+δ (0.00 ≤ x ≤ 0.2, y = 0, 0.1). Lithium occupancy on prismatic Na sites is promoted in Na-deficient (Na < 0.67) PNNMO, evidenced by ex situ and operando synchrotron X-ray diffraction, X-ray absorption spectroscopy, and 7Li solid-state nuclear magnetic resonance. Partial substitution of Na with Li leads to enhanced stability and slightly increased specific capacity compared to PNNMO. In contrast, when lithium is located primarily on octahedral TM sites, capacity is increased but at the cost of stability.

Although liquid mercury (Hg) has been known since antiquity, the formation of stable solid nano forms of Hg at room temperature has not been reported so far. Here, for the first time, we report a simple sonochemical route to obtain solid mercury nanoparticles, stabilized by reduced graphene oxide at ambient conditions. The as-formed solid Hg nanoparticles were found to exhibit remarkable rhombohedral morphology and crystallinity at room temperature. Extensive characterization using various physicochemical techniques revealed the unique properties of the solid nanoparticles of Hg compared to its bulk liquid metal phase. Furthermore, the solid nature of the Hg nanoparticles was studied electrochemically, revealing distinctive properties. We believe that solid Hg nanoparticles have the potential for important applications in the fields of electroanalytical chemistry and electrocatalysis., Formation of the stable solid mercury nanoparticles by acoustic cavitation and their electrochemical activity compared to its bulk liquid metal.

The Hf(OTf)4-catalyzed three-component reaction (3CR) was employed as a powerful tool for facile access to a library of 23 pyrimido[2,1-b][1,3]benzothiazole (PBT)-based AIEgens with full-color tunability, solid-state fluorescence quantum yields of up to 86.8%, and high crystallizability. As atypical propeller-shaped molecules, PBT AIEgens were experimentally determined to dissipate the energy of the excited state via the rotation of the exocyclic carbonyl (ester/ketone) rather than the commonly known phenyl group. Theoretical calculations and crystallographic analysis of PBT AIEgens provide insights into their unique structure–property relationships and AIE mechanism from orbital and molecular aspects, respectively.

Lithium–sulfur batteries are attractive alternatives to lithium-ion batteries because of their high theoretical specific energy and natural abundance of sulfur. However, the practical specific energy and cycle life of Li–S pouch cells are significantly limited by the use of thin sulfur electrodes, flooded electrolytes and Li metal degradation. Here we propose a cathode design concept to achieve good Li–S pouch cell performances. The cathode is composed of uniformly embedded ZnS nanoparticles and Co–N–C single-atom catalyst to form double-end binding sites inside a highly oriented macroporous host, which can effectively immobilize and catalytically convert polysulfide intermediates during cycling, thus eliminating the shuttle effect and lithium metal corrosion. The ordered macropores enhance ionic transport under high sulfur loading by forming sufficient triple-phase boundaries between catalyst, conductive support and electrolyte. This design prevents the formation of inactive sulfur (dead sulfur). Our cathode structure shows improved performances in a pouch cell configuration under high sulfur loading and lean electrolyte operation. A 1-A-h-level pouch cell with only 100% lithium excess can deliver a cell specific energy of >300 W h kg−1 with a Coulombic efficiency >95% for 80 cycles. The shuttling effect in Li–S batteries can be drastically suppressed by using a single-atom Co catalyst and polar ZnS nanoparticles embedded in a macroporous conductive matrix as a cathode. Using this strategy, Li–S pouch cells show stable cycling and high energy performances.

Achieving stable, low-cost electrocatalysts represents a daunting challenge towards practical water oxidation reactions. Here, we report that a degraded electrocatalyst can be revivified under catalytic operating conditions by manipulating reversible phase segregation. Under the oxygen evolution reaction conditions, Fe segregation develops in the Ni–Fe hydroxide host lattice, with the formation of FeOOH, resulting in an interface between the FeOOH and the host lattice. A dynamic metal dissolution–redeposition process accelerates the Fe segregation and formation of the FeOOH secondary phase, resulting in catalyst deactivation. Operando synchrotron spectroscopic and microscopic analyses suggest that the phase segregation is reversible between the water oxidation potential and the catalyst reduction potential. Therefore, we have developed an intermittent reduction methodology to revivify the catalytic activity under the operating conditions, enhancing catalyst durability. The present study highlights that tailoring phase segregation at the catalyst/electrolyte interface constitutes an important strategy for revivifying and stabilizing catalytic activity. Achieving long-term stability of water oxidation electrocatalysts remains a formidable challenge. Now, an in situ electrochemical reduction strategy to revivify mixed Ni–Fe hydroxide catalysts by reversible phase segregation is presented.

The enantioselective ketimine-ene reaction is one of the most challenging stereocontrolled reaction types in organic synthesis. In this work, catalytic enantioselective ketimine-ene reactions of 2-aryl-3H-indol-3-ones with α-methylstyrenes were achieved by utilizing a B(C6 F5 )3 /chiral phosphoric acid (CPA) catalyst. These ketimine-ene reactions proceed well with low catalyst loading (B(C6 F5 )3 /CPA=2 mol %/2 mol %) under mild conditions, providing rapid and facile access to a series of functionalized 2-allyl-indolin-3-ones with very good reactivity (up to 99 % yield) and excellent enantioselectivity (up to 99 % ee). Theoretical calculations reveal that enhancement of the acidity of the chiral phosphoric acid by B(C6 F5 )3 significantly reduces the activation free energy barrier. Furthermore, collective favorable hydrogen-bonding interactions, especially the enhanced N-H⋅⋅⋅O hydrogen-bonding interaction, differentiates the free energy of the transition states of CPA and B(C6 F5 )3 /CPA, thereby inducing the improvement of stereoselectivity.

A central theme of nanocrystal (NC) research involves synthesis of dimension-controlled NCs and studyof size-dependent scaling laws governing their optical, electrical, magnetic, and thermodynamic properties. Here, we describe the synthesis of monodisperse CdO NCs that exhibit high quality-factor (up to 5.5) mid-infrared (MIR) localized surface plasmon resonances (LSPR) and elucidate the inverse scaling relationship between carrier concentration and NC size. The LSPR wavelength is readily tunable between 2.4 and ∼6.0 μm by controlling the size of CdO NCs. Structural and spectroscopic characterization provide strong evidence that free electrons primarily originate from self-doping due to NC surface-induced nonstoichiometry. The ability to probe and to control NC stoichiometry and intrinsic defects will pave the way toward predictive synthesis of doped NCs with desirable LSPR characteristics.

Nickel-iron layered double hydroxide (NiFe LDH) is a promising oxygen evolution reaction (OER) electrocatalyst under alkaline conditions. Much research has been performed to understand the structure-activity relationship of NiFe LDH under OER conditions. However, the specific role of the Fe species remains unclear and under debate. Herein, based on DFT calculations, it was discovered that the edge Fe sites show higher activity towards OER than either the edge Ni sites or lattice sites. Therefore, a facile acid-etching method was proposed to controllably induce the formation of edge Fe sites in NiFe LDH, and the obtained sample exhibited higher OER activity. X-ray absorption near edge structure and extended X-ray absorption fine structure analyses further revealed that the interaction of the edge Fe species with Ni is believed to contribute to the enhancement of the OER performance. This work provides a new understanding of the structure-activity relationship in NiFe LDH and offers a facile method for the design of efficient electrocatalysts in an alkaline environment.

The methane activation and methane dry reforming reactions were studied and compared over 4 wt % Ni/CeO2 and 4 wt % Ni/CeZrO2 (containing 20 wt % Zr) catalysts. Upon the incorporation of Zr into th...

Enhancing the oxygen evolution reaction (OER) performance of NiO materials will greatly expand their applications as low-cost, bifunctional electrocatalysts for water splitting reactions. Introducing stress into the surface layer of catalysts represents an effective method to enhance their catalytic reactivity. Herein, we create compressive stress at the NiOOH/NiO interface using the battery conversion chemistry and in situ Ni to NiOOH transformation. As a result, the OER performance is enhanced by 20 fold compared with that of pure NiO. However, due to the corrosive environment that the electrocatalyst experiences under OER conditions, the stress is released after several CV cycles. The present study demonstrates the importance of interfacial stress that can be produced from in situ surface phase transformation of the electrocatalyst, as well as highlights the challenge of maintaining the mechanical stress under OER conditions during long-term applications.

Atomic-level understanding of the active sites and transformation mechanisms under realistic working conditions is a prerequisite for rational design of high-performance photocatalysts. Here, by using correlated scanning fluorescence X-ray microscopy and environmental transmission electron microscopy at atmospheric pressure, in operando, we directly observe that the (110) facet of a single Cu2O photocatalyst particle is photocatalytically active for CO2 reduction to methanol while the (100) facet is inert. The oxidation state of the active sites changes from Cu(i) towards Cu(ii) due to CO2 and H2O co-adsorption and changes back to Cu(i) after CO2 conversion under visible light illumination. The Cu2O photocatalyst oxidizes water as it reduces CO2. Concomitantly, the crystal lattice expands due to CO2 adsorption then reverts after CO2 conversion. The internal quantum yield for unassisted wireless photocatalytic reduction of CO2 to methanol using Cu2O crystals is ~72%. Photocatalytic reduction of CO2 to methanol offers a promising route to storage of solar energy in the form of chemical fuels. Here, Wu et al. use in operando microscopy to identify the active facets for CO2 reduction on Cu2O and exploit this to obtain high conversion efficiency and selectivity to methanol.

The surface of an electrocatalyst undergoes dynamic chemical and structural transformations under electrochemical operating conditions. There is a dynamic exchange of metal cations between the electrocatalyst and electrolyte. Understanding how iron in the electrolyte gets incorporated in the nickel hydroxide electrocatalyst is critical for pinpointing the roles of Fe during water oxidation. Here, we report that iron incorporation and oxygen evolution reaction (OER) are highly coupled, especially at high working potentials. The iron incorporation rate is much higher at OER potentials than that at the OER dormant state (low potentials). At OER potentials, iron incorporation favors electrochemically more reactive edge sites, as visualized by synchrotron X-ray fluorescence microscopy. Using X-ray absorption spectroscopy and density functional theory calculations, we show that Fe incorporation can suppress the oxidation of Ni and enhance the Ni reducibility, leading to improved OER catalytic activity. Our findings provide a holistic approach to understanding and tailoring Fe incorporation dynamics across the electrocatalyst-electrolyte interface, thus controlling catalytic processes.

Peptidoglycan recognition proteins (PGRPs) are a family of pattern recognition receptors (PRRs) mediating the recognition of peptidoglycan. In the present study, a short-type PGRP gene named Eco-PGRP-S was identified in the orange-spotted grouper (Epinephelus coioides), a major commercial marine fish cultured in Asia. Eco-PGRP-S gene was constitutively expressed in all tissues examined, with the highest expression level observed in gill and skin. As a typical PRR, Eco-PGRP-S is inducible following the stimulation of peptidoglycan, and has an ability to bind peptidoglycan. Importantly, Eco-PGRP-S has been proven to have Zn2+-dependent amidase activity and direct antibacterial activity against Vibrio Harveri and Edwardsiella tarda. In addition, Eco-PGRP-S is mainly localized in cytoplasm and nucleus, and is able to significantly trigger the activation of NF-κB signalling. The present research thus contributes to a better understanding of the molecular mechanism of antibacterial defense and the containment of infectious bacterial diseases in grouper.

Zinc-blende CdS nanoplatelets with atomically flat and very large {100} basal planes terminated solely by one type of element (either Cd or S atoms) are synthesized. Optical spectroscopy, X-ray diffraction, X-ray absorption, and transmission electron microscopy confirm that the surface structures of newly developed S-terminated CdS nanoplatelets are at least as well-defined as the original Cd-terminated nanoplatelets. Band gaps of the nanoplatelets are found to depend on not only the quantum-confined dimension (thickness) but also the nature of the surface termination. The facet structure dictates the packing of the ligands (carboxylate for Cd-terminated nanoplatelets and alkyl for S-terminated nanoplatelets), which causes a difference in the lattice strain and significantly affects the optical spectral width. Experimental and theoretical results reveal that engineering the exciton spatial distribution by the tailored synthesis of semiconductor nanocrystals with a precisely controlled surface structure is fully possible, which should open a new door for delivering the long-promised potential of semiconductor nanocrystals.

The use of 'water-in-salt' electrolytes has considerably expanded the electrochemical window of aqueous lithium-ion batteries to 3 to 4 volts, making it possible to couple high-voltage cathodes with low-potential graphite anodes1-4. However, the limited lithium intercalation capacities (less than 200 milliampere-hours per gram) of typical transition-metal-oxide cathodes5,6 preclude higher energy densities. Partial7,8 or exclusive9 anionic redox reactions may achieve higher capacity, but at the expense of reversibility. Here we report a halogen conversion-intercalation chemistry in graphite that produces composite electrodes with a capacity of 243 milliampere-hours per gram (for the total weight of the electrode) at an average potential of 4.2 volts versus Li/Li+. Experimental characterization and modelling attribute this high specific capacity to a densely packed stage-I graphite intercalation compound, C3.5[Br0.5Cl0.5], which can form reversibly in water-in-bisalt electrolyte. By coupling this cathode with a passivated graphite anode, we create a 4-volt-class aqueous Li-ion full cell with an energy density of 460 watt-hours per kilogram of total composite electrode and about 100 per cent Coulombic efficiency. This anion conversion-intercalation mechanism combines the high energy densities of the conversion reactions, the excellent reversibility of the intercalation mechanism and the improved safety of aqueous batteries.

Purpose Results of some epidemiological studies suggest that moderate alcohol consumption may be associated with a decreased risk to develop NAFLD. Here, the effect of the consumption of moderate beer and diluted ethanol, respectively, on the development of NAFLD were assessed. Methods Female C57BL/6J mice were fed a control diet (C-D) or a diet rich in fructose, fat and cholesterol (FFC) enriched isocalorically and isoalcoholically with beer (FFC + B) or plain ethanol (FFC + E) (2.5 g ethanol/kg body weight/day) for 7 weeks. Liver damage was assessed by histology using NAFLD activity score. Markers of inflammation, insulin resistance and adiponectin signaling were measured at mRNA and protein levels. Using J774A.1 cells as a model of Kupffer cells, the effect of alcoholic beverages on adiponectin receptor 1 (Adipor1) was assessed. Results Hepatic triglyceride concentration, neutrophil granulocytes, iNOS protein concentrations and early signs of insulin resistance found in FFC-fed mice were significantly attenuated in FFC+ B-fed mice (P

Technetium-99 (99Tc) is a major risk driver at nuclear power plants and several US Department of Energy (DOE) sites. Pertechnetate (TcO4−), the most common chemical form present in liquid nuclear waste and the environment, displays limited adsorption onto sediments, making it highly mobile and difficult to immobilize. In this work, inexpensive organoclays and granular activated carbon (GAC) were investigated for TcO4− sequestration from artificial groundwater (AGW). The Tc adsorption capacities were 15 mg/g for organoclays and 25 mg/g for GAC from pH 3–12 AGW under oxic conditions. Competitive NO3− at two orders of magnitude greater concentration than TcO4− reduced the Tc adsorption capacity by only 9–25%. In addition, the adsorbed Tc was effectively desorbed by KI, but not Na2SO4, and the regenerated sorbents retained their Tc removal capacity. X-ray absorption spectroscopy demonstrated that the Tc species bound to the organoclays and GAC was Tc(VII) (i.e., TcO4−), rather than Tc(IV). Thus, the inexpensive organoclays and GAC are highly effective at sequestering 99Tc in its naturally existing TcO4− without requiring costly reductive systems, which may provide a practical solution for removing 99TcO4− from environmental systems.

We developed a general platform for the fabrication of transition metal oxide nanoparticles supported by a graphene foam (GF) by first coating it with a methacrylated gelatin (GelMA) hydrogel, which served as a 3D matrix for nanoparticle dispersion. The engineered GelMA/GF matrix was hydrophilic with good mechanical strength and high conductivity, therefore providing a good platform for the dispersion of a variety of metal/oxide precursors. Due to this platform, well-dispersed Co3O4 nanoparticles with the smallest size of 3 nm assembled on the nitrogen-doped graphene foam (Co3O4/NGF). The crystalline transformation from a CoCl2[H2O]2 precursor to Co3O4 was revealed by in operando X-ray diffraction and absorption techniques. After applying Co3O4/NGF as a free-standing electrocatalyst for water splitting, the nanoparticles of size 3 nm exhibited optimal catalytic activity in alkaline media; the corresponding cell could promote water splitting at a current density of 10 mA cm-2 with only 1.63 V and exhibited excellent stability in a 25 h long-term operation. Our results demonstrate that the GelMA hydrogel-coated 3D graphene foam can be a promising platform for the design and fabrication of graphene-based multifunctional materials.

OBJECTIVE To investigate the association between curcumin and the differentially expressed genes (DEG) in synovial tissues of osteoarthritis. METHODS Microarray analysis was used to screen for the DEG in osteoarthritis synovial cells. Curcumin-related genes were identified through the drug-gene interaction network STITCH (http://stitch.embl.de/cgi/input.pl). Expression levels of fibronectin 1 (FN1) and collagen III protein were measured by western blot. MTT assay was used to examine the effects of different concentrations of curcumin on cell viability. Western blot and quantitative real-time polymerase chain reaction were used to validate the different expression levels of matrix metalloproteinase-3 (MMP3). Clone formation assay, flow cytometry, and the TUNEL method were conducted for detecting the cell proliferation and apoptosis rate. RESULTS In the two chips of GSE1919 and GSE55235, the average expression of MMP3 in the osteoarthritis group was 63.7% and 12.9% higher than that of the healthy control, respectively. The results of western blot also showed that the average expression of MMP3 in 30 osteoarthritis patients was 132% higher than that of the healthy group, which confirmed that MMP3 was highly expressed in osteoarthritis group. The results of MTT showed that at 72 h, the cell viability of 40 μmol/L curcumin was the lowest and 79.6% lower than for the 0 μmol/L group, so the final curcumin concentration of 40 μmol/L was selected for subsequent experiments. Western blot results further showed that the expression of MMP3 was 44% lower in the untreated groups compared with the curcumin group, and the expressions of FN1 and collagen III were increased by 112% and 84%, respectively, which indicated that curcumin inhibited MMP3 expression and decreased osteoarthritis synovial cell activity. Cloning formation experiments showed that cell numbers increased by 75% and 20.5% in untreated and curcumin groups, and compared with the untreated group, the cells in the curcumin group decreased by 30.8%. Flow cytometry showed that the apoptotic rate in the curcumin group increased by 85.1% compared with the untreated group, but for a single group, MMP3 decreased the apoptotic rate by 53.9% and 46.7%, respectively. CONCLUSIONS MMP3 was highly expressed in osteoarthritis synovial cells. Curcumin could reduce cell viability, inhibit cell proliferation, increase cell apoptosis, and eventually alleviate inflammation of osteoarthritis by inhibiting the expression of MMP3.

A robust porous structure is often needed for practical applications in electrochemical devices, such as fuel cells, batteries, and electrolyzers. While templating approach is useful for the preparation of porous materials in general, it is not effective for the synthesis of oxide-based electrocatalysts owing to the chemical instability of disordered porous materials thus created. Now the synthesis of phase-pure porous yttrium ruthenate pyrochlore oxide using an unconventional porogen of perchloric acid is presented. The lattice oxygen defects are formed by the mixed-valence state of Ru4+/5+ through the partial substitution of Ru4+ with Y3+ cations, leading to the formation of mixed B-site Y2 [Ru1.6 Y0.4 ]O7-δ . This porous Y2 [Ru1.6 Y0.4 ]O7-δ electrocatalyst exhibits a turnover frequency (TOF) of 560 s-1 (at 1.5 V versus RHE) for the oxygen evolution reaction, which is two orders of magnitude higher than that of the RuO2 reference catalyst (5.41 s-1 ).

In this article, carbon nanotubes (CNTs) was modified with conducting polymer polyaniline (PANI) to produce composite supporters (PANI-CNTs), and then the MnO2/PANI-CNTs composite material was prep...

The addition of plant oils such as soybean oil (S) to a diet rich in saturated fatty acids is discussed as a possible route to prevent or diminish the development of metabolic disease. Here, we assessed whether a butterfat-rich diet fortified with S affects the development of early non-alcoholic steatohepatitis (NASH) and glucose intolerance. Female C57BL/6J mice were fed a standard-control diet (C), a fat-, fructose-, and cholesterol-rich diet (FFC, 25E% butterfat, 50% (wt./wt.) fructose, 0.16% (wt./wt.) cholesterol), or FFC supplemented with S (FFC + S, 21E% butterfat + 4E% S) for 13 weeks. Indicators of liver damage, inflammation, intestinal barrier function, and glucose metabolism were measured. Lipopolysaccharide (LPS)-challenged J774A.1 cells were incubated with linolenic and linoleic acids (ratio 1:7.1, equivalent to S). The development of early NASH and glucose intolerance was significantly attenuated in FFC + S–fed mice compared to FFC-fed mice associated with lower hepatic toll-like receptor-4 mRNA expression, while markers of intestinal barrier function were significantly higher than in C-fed mice. Linolenic and linoleic acid significantly attenuated LPS-induced formation of reactive nitrogen species and interleukin-1 beta mRNA expression in J774A.1 cells. Our results indicate that fortifying butterfat with S may attenuate the development of NASH and glucose intolerance in mice.

The sodium superionic conductor (NASICON)-type Na3V2(PO4)3 (NVP) with 3D framework is a promising candidate in sodium ion batteries. Plenty of subsequent modification methods are reported. However, the research of selection of carbon resources is few investigated. To explore the significant effects of different carbon resources on the sodium storage property of NVP system, herein, two kinds of carbon resources, such as citric acid and oxalic acid, are chosen to prepare the carbon coated NVP/C system utilizing a facile sol-gel route. The effects of different raw materials on the crystal structure, morphological features, kinetic characteristics and electrochemical property are deeply explored. The results demonstrate that the optimized NVP/C composite generated by citric acid possesses a larger crystal cell volume and a smaller particle size morphology, which brings the favorable expanded channel and shortened pathway for Na+ migration, resulting in superior kinetic characteristics. Accordingly, the citric acid induced NVP/C electrode exhibits a significantly improved sodium storage property. As a consequence, it delivers a high capacity of 112.3 mAh g−1 at 0.1 C. The retention ratio is nearly 100% cycled at 1 C rate after 200 cycles. Favored by the rapid electron and ion transfer, distinct reversible capacities of 90.0 and 89.1 mAh g−1 are obtained at 2 and 5 C rate, accompanied by high retention of 92.7% and 90.0% after 200 cycles. Therefore, this modified NVP/C material is a promising cathode for practical applications.

Excessive cerebral inflammation plays a key role in early brain injury (EBI) after subarachnoid hemorrhage (SAH). Berberine, an isoquinoline alkaloid isolated from Chinese herb Coptis chinensis, possesses anti-inflammatory, and neuroprotective effects. Here we evaluated the beneficial effects of berberine against SAH-induced inflammatory response and the subsequent brain injury. Our data showed that berberine treatment significantly inhibited microglia activation and proinflammatory cytokines release. Concomitant with suppressed cerebral inflammation, berberine mitigated the subsequent brain injury as demonstrated by improved neurological behavior, reduced brain edema, and decreased neural apoptosis. Moreover, berberine significantly inhibited high mobile group box 1 (HMGB1)/nuclear factor-κB (Nf-κB)-dependent pathway and enhanced sirtuin 1 (SIRT1) expression after SAH. Treatment with ex527, a selective SIRT1 inhibitor, reversed berberine-induced SIRT1 activation and inhibitory effects on HMGB1/Nf-κB activation. In addition, ex527 pretreatment abated the anti-inflammatory and neuroprotective effects of berberine on SAH. Taken together, these findings suggest that berberine provides beneficial effects against SAH-triggered cerebral inflammation by inhibiting HMGB1/Nf-κB pathway, which may be modulated by SIRT1 activation.

Dietary fat is discussed to be critical in the development of non-alcoholic fatty liver disease. Here, we assess the effect of exchanging dietary fat source from butterfat to extra virgin olive oil on the progression of an already existing diet-induced non-alcoholic fatty liver disease in mice. Female C57BL/6J mice were fed a liquid butterfat-, fructose- and cholesterol-rich diet (BFC, 25E% from butterfat) or control diet (C, 12%E from soybean oil) for 13 weeks. In week 9, fat sources of some BFC- and C-fed mice were switched either to 25E% or 12E% olive oil (OFC and CO). Glucose and insulin tolerance tests were performed, and markers of liver damage and glucose metabolism were assessed. After 6 weeks of feeding, BFC-fed mice had developed marked signs of insulin resistance, which progressed to week 12 being not affected by the exchange of fat sources. Liver damage was similar between BFC- and OFC-fed mice. Markers of lipid metabolism and lipid peroxidation in liver and of insulin signaling in liver and muscle were also similarly altered in BFC- and OFC-fed mice. Taken together, our data suggest that exchanging butterfat with extra virgin olive oil has no effect on the progression of non-alcoholic fatty liver disease and glucose tolerance in mice.

Sodium butyrate (SoB) supplementation has been suggested to attenuate the development of non-alcoholic fatty liver disease (NAFLD). Here, we determined the therapeutic potential of SoB on NAFLD progression and molecular mechanism involved. Eight-week old C57BL/6J mice were pair-fed a fat-, fructose- and cholesterol-rich diet (FFC) or control diet (C). After 8 weeks, some mice received 0.6g SoB/kg bw in their respective diets (C+SoB, FFC+SoB) or were maintained on C or FFC for the next 5 weeks of feeding. Liver damage, markers of glucose metabolism, inflammation, intestinal barrier function and melatonin metabolism were determined. FFC-fed mice progressed from simple steatosis to early non-alcoholic steatohepatitis, along with significantly higher TNF&alpha, and IL-6 protein levels in the liver and impaired glucose tolerance. In FFC+SoB-fed mice, disease was limited to steatosis associated with protection against the induction of Tlr4 mRNA and iNOS protein levels in livers. SoB supplementation had no effect on FFC-induced loss of tight junction proteins in the small intestine but was associated with protection against alterations in melatonin synthesis and receptor expression in the small intestine and livers of FFC-fed animals. Our results suggest that the oral supplementation of SoB may attenuate the progression of simple steatosis to steatohepatitis.

Background and Aims:General overnutrition, and a diet rich in fat and sugar are among the key risk factors for the development of metabolic diseases including diabetes type 2 and non-alcoholic fatty liver diseases (NAFLD). While being among the most commonly consumed oils world-wide, the effects of soybean oil on the development of metabolic diseases are yet not understood. Indeed, existing data is in part contradictory. Based on this background, the aim of the present study was to investigate the effects of soybean oil consumption on the development of non-alcoholic steatohepatitis (NASH), the more progressed stage of NAFLD, and insulin resistance.Methods:Female C57BL/6J mice were fed either a liquid standard control diet (C) or a liquid fat-, fructose- and cholesterol-rich diet (FFC, 25E% butterfat, 50% (wt/wt) fructose, 0.155% (wt/wt) cholesterol) or a FFC supplemented with soybean oil (FFC + S, 21E% butterfat + 4E% soy oil), with FFC and FFC + S-fed groups being pair fed for 13 weeks to induce steatohepatitis. After 7 and 12 weeks of feeding, a glucose tolerance test was performed. Indicators of liver damage, inflammation, intestinal barrier function and markers of insulin signaling cascade were measured in intestinal, liver and muscle tissue.Results:As expected FFC-fed mice developed early signs of NASH and insulin resistance. Despite similar caloric intake and body weight gain, development of NASH and insulin resistance were significantly attenuated in FFC + S-fed mice when compared to FFC-fed animals. Indeed, signs of hepatic inflammation e.g. number of inflammatory foci and neutrophils as well as activity of transaminase in plasma were almost at the level of control in FFC + S-fed mice. Prevalence of macrovesicular steatosis being the predominant type of fat accumulation found in FFC-fed animals was also markedly lower in FFC + S-fed mice. Furthermore, while in muscle and liver tissue of FFC-fed mice insulin receptors mRNA expression was significantly different from C-fed animals, insulin receptors expression in FFC + S-fed mice was almost at the level of controls. The protective effects of soybean oil supplementation on the development of metabolic alterations were associated with a protection against the induction of TLR4 mRNA expression and dependent signaling molecules in liver tissue.Conclusion:Taking together, our results indicate that supplementation with soybean oil may attenuate the development of diet-induced NASH and insulin resistance in mice and that this may be related to alteration of TLR4-dependent signaling cascade in liver tissue. (Funded in parts by UFOP e.V.)

The chemical asymmetry at the hetero-structure interface offers an effective opportunity to design desirable electronic structures by controlling charge transfer and orbital hybridization across the interface. However, controlling the hetero-interface remains a daunting task. Here, we report the modulation of interfacial coupling of (La0.67Sr0.33MnO3)n/(SrTiO3)n superlattices by manipulating the periodic thickness with n unit cells of SrTiO3 and n unit cells of La0.67Sr0.33MnO3 with a fixed thickness of ~120 unit cells. The easy axis of magnetic anisotropy rotates ~45° towards the out-of-plane direction from n = 10 to n = 2 at reduced temperature TRe = T/TS = 0.87, where TS is the temperature at the onset of magnetization. Transmission electron microscopy reveals an enlarged tetragonal ratio >1 with breaking of volume conservation around the (La0.67Sr0.33MnO3)n/(SrTiO3)n interface and electronic charge transfer from Mn to Ti 3d orbitals across the interface. Orbital hybridization accompanying the charge transfer results in preferred occupancy of $${3d}_{3z^2-r^2}$$ orbitals at the interface and induces a stronger electronic hopping integral and interfacial magnetic anisotropy along the out-of-plane direction, which contributes to the rotation towards the out-of-plane direction of an effective magnetic easy axis for n = 2. We demonstrate that interfacial orbital hybridization with charge transfer in the superlattice of strongly correlated oxides may be a promising approach to tailor electronic and magnetic properties in device applications. A composite material with tuneable magnetic properties which could add novel functionality to electronic devices has been developed by scientists from Singapore and the USA. The interface between two crystalline materials can exhibit properties differing from those of either substance separately. These interface properties can be extended to three dimensions by stacking alternating thin layers of the two materials, creating a so-called superlattice. Bangmin Zhang from the National University of Singapore and co-workers used this concept to alter the magnetic response of a superlattice consisting of lanthanum strontium manganite and strontium titanate. They showed that they could rotate the direction along which the smallest magnetic field is required to magnetize the material by changing the thickness of the layers. This could be useful in devices that are controlled by interaction between electric and magnetic fields. The modulation of interfacial coupling of (La0.67Sr0.33MnO3)n/(SrTiO3)n superlattices with n unit cells of SrTiO3 and n unit cells La0.67Sr0.33MnO3, offers an effective opportunity to control charge transfer and orbital hybridization. The easy axis of magnetic anisotropy rotates ~45° towards the out-of-plane direction from n = 10 to n = 2 at reduced temperature TRe = T/TS = 0.87 (TS is onset of magnetization). Orbital hybridization accompanying the charge transfer results in preferred occupancy of $$3d_{3z_{2} - r_{2}}$$ orbital at the interface, and induces stronger electronic hopping integral and interfacial magnetic anisotropy along perpendicular direction, useful to tailor properties in device applications.

Glucose isomerase (GI) responsible for catalyzing the isomerization from d-glucose to d-fructose, was an important enzyme for producing high fructose corn syrup (HFCS). In a quest to prepare HFCS at elevated temperature and facilitate enzymatic recovery, an effective procedure for whole cell immobilization of refractory Thermus oshimai glucose isomerase (ToGI) onto Celite 545 using tris(hydroxymethyl)phosphine (THP) as crosslinker was established. The immobilized biocatalyst showed an activity of approximate 127.3 U/(g·immobilized product) via optimization in terms of cells loading, crosslinker concentration and crosslinking time. The pH optimum of the immobilized biocatalyst was displaced from pH 8.0 of native enzyme to neutral pH 7.0. Compared with conventional glutaraldehyde (GLU)-immobilized cells, it possessed the enhanced thermostability with 70.1% residual activity retaining after incubation at 90°C for 72 h. Moreover, the THP-immobilized biocatalyst exhibited superior operational stability, in which it retained 85.8% of initial activity after 15 batches of bioconversion at 85°C. This study paved a way for reducing catalysis cost for upscale preparation of HFCS with higher d-fructose concentration.

Venom injected into the host plays vital roles in facilitating successful parasitization and development for parasitoid wasps, especially those devoid of polydnavirus, and the abundant venom proteins appear to be most likely involved in parasitization success. Previously, we found the four most abundant venom proteins, including 4-coumarate:CoA ligase-like 4 (4CL4-like), in the Tetrastichus brontispae (Hymenoptera: Eulophidae) venom apparatus. In this study, we cloned, expressed T. brontispae 4CL4-like (Tb4CL4-like) in Escherichia coli, and investigated its immunosuppressive properties. The deduced amino acid sequence for Tb4CL4-like shares high identity at conserved amino acids associated with the acyl-activating enzyme (AAE) consensus motif but shows only &lt, 40% identity with the members in the AAE superfamily. mRNA abundance analysis indicated that Tb4CL4-like was transcribed mainly in the venom apparatus. Recombinant Tb4CL4-like inhibited Octodonta nipae (Coleoptera: Chrysomelidae) pupal cellular encapsulation and spreading by targeting the hemocyte cytoskeleton and reduced the hemocyte-mediated phagocytosis of E. coli in vivo. Moreover, Tb4CL4-like exhibited greater affinity to palmitic acid and linolenic acid based on the molecular docking assay and is hypothesized to be involved in fatty acid metabolism. In conclusion, our results suggest that Tb4CL4-like may be an immunity-related AAE protein that is involved in the regulation of host immunity through fatty acid metabolism-derived signaling pathways.

Sodium-ion batteries are attractive for large-scale energy storage due to the abundance of sodium, but the deficient capacity achieved by cathode materials prevents their further applications. Chemical substitution of Na in transition metal layers is a promising solution to utilize both the cationic and anionic redox activities for boosting energy storage. Unfortunately, different from the classic Li-rich Li2MnO3, a pure prototype with anionic redox activity has not been found among the typical Na-rich cathodes. Herein, we originally design a Na-rich layered oxide prototype, namely Na3RuO4 (Ru5+), which delivers a partial reversible capacity solely via the participation of oxygen anions. More importantly, the anionic redox activity is validated by the in situ Raman observation of reversible peroxo-based O–O (de)bonding upon cycling. Our findings not only highlight the multiple electron-transfer strategy for capacity extension, but also broaden the horizon in designing Na-rich electrode materials for high-energy sodium-ion batteries.

A series of indole-based [1,2,4]triazolo [4,3-a]pyridine derivatives was designed and synthesized as novel microtubulin polymerization inhibitors by using a conformational restriction strategy. These compounds exhibited moderate to potent anti-proliferative activities against a panel of cancer cell lines (HeLa, A549, MCF-7 and HCT116). Among them, compound 12d featuring a N-methyl-5-indolyl substituent at the C-6 position of the [1,2,4]triazolo [4,3-a]pyridine core exhibited the highest antiproliferative activity with the IC50 values ranging from 15 to 69 nM, and remarkable inhibitory effect on tubulin polymerization with an IC50 value of 1.64 μM. Mechanistic studies revealed that compound 12d induced cellular apoptosis and cell cycle arrest at the G2/M phase in a dose-dependent fashion. Moreover, compound 12d significantly suppressed wound closure and disturbed microtubule networks.

Background: Universally accepted therapeutic strategies for the treatment of nonalcoholic steatohepatitis (NASH) are still lacking. Studies suggest a preventive effect of oral Gln supplementation on the development of NASH; however, whether Gln also has therapeutic potential for pre-existing NASH has not yet been clarified.Objective: The aim of the present study was to determine whether Gln prevents the progression of diet-induced NASH in mice.Methods: For 8 wk, female C57BL/6J mice (6-8 wk old) were pair-fed a liquid Western-style diet [WSD, 25% of energy from fat, 50% wt:wt fructose, 0.16% wt:wt cholesterol] or control diet (C diet) to induce liver damage. From week 8 to 13, they were pair-fed the C diet or WSD alone or supplemented with l-Gln to provide 2.1 g/kg body weight (C diet + Gln or WSD + Gln). Energy intake was adjusted to the group with the lowest energy intake. Indexes of liver damage and inflammation, intestinal barrier function, and toll-like receptor 4 (Tlr4) signaling in the liver were determined.Results: The liver histology scores significantly increased from 8 to 13 wk (+31%) in WSD-fed mice and were significantly higher than in controls (P ≤ 0.05 for both time comparisons), whereas scores did not differ between C diet-fed and WSD + Gln-fed mice after 13 wk of feeding. The occludin protein concentrations in the small intestinal tissue were similarly reduced in both WSD-fed groups when compared with controls [WSD compared with C diet (-53%) and C diet + Gln (-42%), P ≤ 0.05; WSD + Gln compared with C diet + Gln (-34%), P ≤ 0.05] after 13 wk, whereas the expression of myeloid differentiation primary response gene 88 mRNA and concentration of inducible nitric oxide synthase and 4-hydroxynonenal protein adducts were significantly higher only in livers of WSD-fed mice (P ≤ 0.05 for the WSD group compared with all other groups; WSD + Gln group compared with the C diet groups: NS).Conclusion: Taken together, our data suggest that oral Gln supplementation protects mice from the progression of pre-existing, WSD-induced NASH.

Non-alcoholic fatty liver disease (NAFLD) is by now the most prevalent liver disease worldwide. The non-proteogenic amino acid l-citrulline (L-Cit) has been shown to protect mice from the development of NAFLD. Here, we aimed to further assess if L-Cit also attenuates the progression of a pre-existing diet-induced NAFLD and to determine molecular mechanisms involved. Female C57BL/6J mice were either fed a liquid fat-, fructose- and cholesterol-rich diet (FFC) or control diet (C) for 8 weeks to induce early stages of NASH followed by 5 more weeks with either FFC-feeding +/- 2.5 g L-Cit/kg bw or C-feeding. In addition, female C57BL/6J mice were either pair-fed a FFC +/- 2.5 g L-Cit/kg bw +/- 0.01 g/kg bw i.p. N(ω)-hydroxy-nor-l-arginine (NOHA) or C diet for 8 weeks. The protective effects of supplementing L-Cit on the progression of a pre-existing NAFLD were associated with an attenuation of 1) the increased translocation of bacterial endotoxin and 2) the loss of tight junction proteins as well as 3) arginase activity in small intestinal tissue, while no marked changes in intestinal microbiota composition were prevalent in small intestine. Treatment of mice with the arginase inhibitor NOHA abolished the protective effects of L-Cit on diet-induced NAFLD. Our results suggest that the protective effects of L-Cit on the development and progression of NAFLD are related to alterations of intestinal arginase activity and intestinal permeability., Graphical abstract Image 1, Highlights • l-citrulline diminished progression of non-alcoholic fatty liver disease (NAFLD). • l-citrulline protects from fructose-induced small intestinal barrier dysfunction. • NASH development is associated with a loss of arginase activity in small intestine. • l-citrulline improves intestinal arginase activity in diet-induced NAFLD. • Arginase inhibitor attenuates effects of l-citrulline on NAFLD development.

We used direct-rate measurements and reflection absorption infrared spectroscopy (RAIRS) to investigate CO oxidation on a PdO(101) film at 450 K and focused on characterizing how the gas-phase composition (O2 + CO) influences the reaction kinetics and the coupling between the reaction and the surface phases that develop. We find that chemisorbed O atoms on Pd(111) are intrinsically more reactive than PdO(101) and that CO oxidation rates can be as much as 2–3 times higher on Pd(111) compared with PdO(101) for the conditions studied. Using RAIRS, we show that reduction of PdO(101) by CO produces metallic Pd(111) domains at 450 K and identified several rate processes that couple the PdO(101) and Pd(111) phases during reaction, including the formation of Pd(111) domains from O vacancies on PdO(101), oxygen transfer from the oxide to the metal to generate chemisorbed O atoms, and the healing of surface oxygen vacancies on PdO(101) via O atom migration from the bulk oxide as well as O2 dissociative adsorption. ...

The extraction of chromate from chromite via the sulfuric acid leaching process has strong potential for practical use because it is a simple and environmentally friendly process. This paper aims to study the sulfuric acid leaching process using chromite as a raw material via either microwave irradiation or in the presence of an oxidizing agent. The results show that the main phases in Pakistan chromite are ferrichromspinel, chrompicotite, hortonolite, and silicate embedded around the spinel phases. Compared with the process with an oxidizing agent, the process involving microwaves has a higher leaching efficiency. When the mass fraction of sulfuric acid was 80% and the leaching time was 20 min, the efficiency could exceed 85%. In addition, the mechanisms of these two technologies fundamentally differ. When the leaching was processed in the presence of an oxidizing agent, the silicate was leached first and then expanded. By contrast, in the case of leaching under microwave irradiation, the chromite was dissolved layer by layer and numerous cracks appeared at the particle surface because of thermal shock. In addition, the silicate phase shrunk instead of expanding.

Silicon carbide fiber-reinforced silicon carbide matrix composites have been investigated for their use as structural materials for advanced nuclear reactor. Although quite a number of researches have been devoted to probe the effects of irradiation on various properties of the composites, there is little known about the atomistic mechanism for irradiation resistance. In this study, a two-temperature model has been used to investigate the irradiation damage of SiC/Gra/SiC composites, which includes three parts and two SiC/C interfaces, two single crystal cubic silicon carbide on two sides and a few graphene sheets in the middle part. By simulating 100 keV displacement cascades, we find that the number of defects in the reinforcement is larger than that in the matrix, which indicates the damage in the reinforcement is more serious than that in the matrix. Moreover, we explicitly investigate the damage behavior of the interphase graphene layers and find that some atoms in one graphene sheet form many new chemical bonds with atoms in another one, which leads to the transition from sp 2 to sp 3 hybridization. The newly formed chemical bonds link the different graphene layers and make graphene-like electronic structure more “diamond-like”, enhancing the irradiation resistance of the matrix.

Here we report the syntheses of largely unexplored lead and bismuth chalcogenidometallates in the solution phase. Using N2H4 as the solvent, new compounds such as K6Pb3Te6·7N2H4 were obtained. These soluble molecular compounds underwent cation exchange processes using resin chemistry, replacing Na+ or K+ by decomposable N2H5+ or tetraethylammonium cations. They also transformed into stoichiometric lead and bismuth chalcogenide nanomaterials with the addition of metal salts. Such a versatile chemistry led to a variety of composition-matched solders to join lead and bismuth chalcogenides and tune their charge transport properties at the grain boundaries. Solution-processed thin films composed of Bi0.5Sb1.5Te3 microparticles soldered by (N2H5)6Bi0.5Sb1.5Te6 exhibited thermoelectric power factors (∼28 μW/cm K2) comparable to those in vacuum-deposited Bi0.5Sb1.5Te3 films. The soldering effect can also be integrated with attractive fabrication techniques for thermoelectric modules, such as screen printing, sugg...

Background and aim It has been suggested in several studies that an increased translocation of bacterial lipopolysaccharide (LPS) and, subsequently, an activation of toll-like receptor (TLR)-dependent signaling pathways in the liver may contribute to the development of non-alcoholic fatty liver disease. Methods Eight-week-old lipopolysaccharide-binding protein (LBP)-/- and wild-type (WT) mice were pair fed either a liquid diet rich in fat, fructose, and cholesterol (Western-style diet [WSD]) or a control liquid diet for 8 weeks. Parameters of liver injury, markers of TLR-4-dependent signaling pathway, and glucose/lipid metabolism were determined. Results Despite similar total caloric intake, weight gain, fasting blood glucose levels, and liver-to-bodyweight ratio, indices of liver damage determined by liver histology and transaminases were markedly lower in WSD-fed LBP-/- mice than in WSD-fed WT animals. In line with these findings, number of neutrophils, F4/80 positive cells, and plasminogen activator inhibitor 1 were only found to be significantly increased in livers of WSD-fed WT mice. While mRNA expressions of TLR-4 and myeloid differentiation primary response 88 were similar between WSD-fed groups, concentrations of inducible nitric oxide synthase protein and 4-hydroxynonenal protein adducts were significantly higher in livers of WSD-fed WT mice than in WSD-fed LBP-/- animals. Markers of lipid metabolism, for example, sterol regulatory element-binding protein 1c and fatty acid synthase per se, were significantly lower in livers of LBP-/- mice; however, mRNA expressions did not differ between controls and WSD-fed mice within the respective mouse strain. Conclusion Taken together, our results suggest that LBP is a critical factor in the development of non-alcoholic fatty liver disease in mice.

We investigate the effect of several coatings applied in biomedical applications to iron oxide nanoparticles on the size, structure and composition of the particles. The four structural techniques employed - TEM, DLS, VSM, SAXS and EXAFS - show no significant effects of the coatings on the spherical shape of the bare nanoparticles, the average sizes or the local order around the Fe atoms. The NPs coated with hydroxylmethylene bisphosphonate or catechol have a lower proportion of magnetite than the bare and citrated ones, raising the question whether the former are responsible for increasing the valence state of the oxide on the NP surfaces and lowering the overall proportion of magnetite in the particles. VSM measurements show that these two coatings lead to a slightly higher saturation magnetization than the citrate. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazu and Dr. Federica Migliardo. (C) 2016 Elsevier B.V. All rights reserved.

Super-hydrophobic Co3O4-loaded nickel foam with two different morphologies were successfully prepared via a novel and simple method. The nano-flower and nano-flake structure was respectively generated on the surface of commercial nickel foam surface via hydrothermal treatment and then was modified with the perfluorinated alkyl silane reagent (PFAS). The samples were characterized by X-ray spectroscopy (XRD), Fourier transform infrared spectrometer (FT-IR), scanning electron microscopy (SEM), N2-physorption and water contact angle (WCA) meter. The results showed the Co3O4-loaded nickel foam possessed well super-hydrophobic and excellent corrosion-resistant properties after immersed in NaCl solution (3.5 wt.%), hydrochloric acid solution (pH = 1) and sodium hydroxide solution (pH = 14) each for 7 days in sequence. The water contact angle (WCA) of the corroded samples can reach 155°, and CAH (slide angle) are

The purpose of this study was to investigate the effects of scaffold surface morphology on cell adhesion and survival rate in vitreous cryopreservation of tenocyte-scaffold constructs. Tenocytes were obtained from tail tendons of rats. Polydimethylsiloxane (PDMS) was used to fabricate three types of scaffolds with varying surface morphological characteristics, i.e., smooth, micro-grooved, and porous surfaces, respectively. The tenocytes were seeded on the surfaces of the scaffolds to form tenocyte-scaffold constructs. The constructs were cryopreserved in a vitreous cryoprotectant (CPA) with a multi-step protocol. The cell adhesion to scaffolds was observed with electronic scanning microscopy (SEM). The elongation index of the living tenocytes and ratio of live/dead cell number were examined based on a live/dead dual fluorescent staining technique, and the survival rate of tenocytes was studied with flow cytometry (FC). The results showed the shapes of tenocytes varied between the different groups: flat or polygonal (on smooth surface), spindle (on micro-grooved surface), and spindle or ellipse (on porous surface). After thawing, the porous surface got the most living tenocytes and a higher survival rate, suggesting its potential application for vitreous cryopreservation of engineered tendon constructs.

Calcium oxide-based expansive additive (CEA) has the disadvantages of a too-fast reaction rate when mixed with water and lower storage stability when exposed to the atmosphere, which reduces its expansion efficiency for shrinkage-compensating concrete. This paper introduces a modification technology by encapsulating CEA particles with polylactic acid (PLA) polymer to form a protective membrane. Experimental results indicate that the encapsulating PLA membrane could build an inductive period in the hydration process of CEA and delay the initiation of hydration when mixed with water, thus effectively reducing the invalid hydration of CEA during the plastic stage. Restrained and free deformation testing results demonstrate that the expansion of the cement paste incorporating modified CEA increases by 25% and 35% over that of the paste with the original CEA, respectively. The weathering rate, assessed under conditions of 25°C and 60% humidity to evaluate the storage stability, was slowed down by 30%. This paper offers an original method to improve the expansion efficiency of additives so that sufficient varieties of polymer can be utilised.

The development of cost-effective catalysts with both high activity and selectivity for carbon-oxygen bond activation is a major challenge and has important ramifications for making value-added chemicals from carbon dioxide (CO

The spin state transition from low spin to high spin upon substrate addition is one of the key steps in cytochrome P450 catalysis. External perturbations such as pH and hydrogen bonding can also trigger the spin state transition of hemes through deprotonated histidine (e.g. Cytochrome c). In this work, we report the isolated 2-methylimidazole Cobalt(II) [Co(TPP)(2-MeHIm)] and [Co(TTP)(2-MeHIm)], and the corresponding 2-methylimidazolate derivatives where the N−H proton of axial 2-MeHIm is removed. Interestingly, various spectroscopies including EPR and XAFS determine a high-spin state (S = 3/2) for the imidazolate derivatives, in contrast to the low-spin state (S = 1/2) of all known imidazole analogs. DFT assisted stereoelectronic investigations are applied to understand the metal-ligand interactions, which suggest that the dramatically displaced metal center allowing a promotion eg(dπ) → b1g(\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$d_{x^2 - y^2}$$\end{document}dx2-y2) is crucial for the occurrence of the spin state transition., Studying the electronic structures and spin transitions of synthetic heme analogs is crucial to advancing our understanding of heme enzyme mechanisms. Here the authors show that a Co(II) porphyrin complex undergoes an unexpected spin state transition upon deprotonation of its axial imidazole ligand.

Hepatic ammonia handling was analyzed in taurine transporter (TauT) KO mice. Surprisingly, hyperammonemia was present at an age of 3 and 12 months despite normal tissue integrity. This was accompanied by cerebral RNA oxidation. As shown in liver perfusion experiments, glutamine production from ammonia was diminished in TauT KO mice, whereas urea production was not affected. In livers from 3-month-old TauT KO mice protein expression and activity of glutamine synthetase (GS) were unaffected, whereas the ammonia-transporting RhBG protein was down-regulated by about 50%. Double reciprocal plot analysis of glutamine synthesis versus perivenous ammonia concentration revealed that TauT KO had no effect on the capacity of glutamine formation in 3-month-old mice, but doubled the ammonia concentration required for half-maximal glutamine synthesis. Since hepatic RhBG expression is restricted to GS-expressing hepatocytes, the findings suggest that an impaired ammonia transport into these cells impairs glutamine synthesis. In livers from 12-, but not 3-month-old TauT KO mice, RhBG expression was not affected, surrogate markers for oxidative stress were strongly up-regulated, and GS activity was decreased by 40% due to an inactivating tyrosine nitration. This was also reflected by kinetic analyses in perfused liver, which showed a decreased glutamine synthesizing capacity by 43% and a largely unaffected ammonia concentration dependence. It is concluded that TauT deficiency triggers hyperammonemia through impaired hepatic glutamine synthesis due to an impaired ammonia transport via RhBG at 3 months and a tyrosine nitration-dependent inactivation of GS in 12-month-old TauT KO mice.

The antidiabetic drug metformin has been proposed to affect non-alcoholic fatty liver disease (NAFLD) through its effects on intestinal microbiota and barrier function. However, so far most studies focused on long-term effects and more progressed disease stages. The aim of this study was to assess in two experimental settings, if the onset of NAFLD is associated with changes of intestinal microbiota and barrier function and to determine effects of metformin herein. C57Bl/6J mice were fed a liquid control diet (C) or fat-, fructose- and cholesterol-rich diet (FFC) for four days or six weeks ±300 mg/kg BW/day metformin (Met). Markers of liver health, intestinal barrier function and microbiota composition were assessed. Metformin treatment markedly attenuated FFC-induced NAFLD in both experiments with markers of inflammation and lipidperoxidation in livers of FFC + Met-fed mice being almost at the level of controls. Metformin treatment attenuated the loss of tight junction proteins in small intestine and the increase of bacterial endotoxin levels in portal plasma. Changes of intestinal microbiota found in FFC-fed mice were also significantly blunted in FFC + Met-fed mice. Taken together, protective effects of metformin on the onset of NAFLD are associated with changes of intestinal microbiota composition and lower translocation of bacterial endotoxins.

Background Non-alcoholic fatty liver disease (NAFLD) is one of the most common liver diseases worldwide lacking universally accepted therapies. Studies suggest that coffee consumption is associated with a reduced risk of NAFLD; however, molecular mechanisms and ingredients involved remain to be fully understood. Here, we determined the effects of regular intake of decaffeinated coffee on the development of NAFLD in mice, and molecular mechanisms involved. Methods Female C57BL/6J mice (n = 6–7/ group) were pair-fed either a liquid control diet (C) or fat-, fructose- and cholesterol-rich diet (FFC) +/- decaffeinated coffee (DeCaf, 6 g/kg BW) for 4 days or 6 weeks. Indices of liver damage, hepatic inflammation and parameters of insulin resistance and intestinal permeability as well as nitric oxide system were determined. Results Early signs of insulin resistance and non-alcoholic steatohepatitis (NASH) found after 6 weeks of FFC feeding were significantly lower in FFC+DeCaf-fed mice when compared to FFC-fed animals. Moreover, elevation of portal endotoxin levels and loss of tight junction proteins in proximal small intestine found in FFC-fed mice were significantly attenuated in FFC+DeCaf-fed animals. These beneficial effects of DeCaf were associated with a protection against the significant induction of inducible NO-synthase protein levels and 3-nitrotyrosine protein adducts found in proximal small intestine of FFC-fed mice. Similar protective effects of DeCaf were also found in mice fed the FFC diet short-term. Conclusion Our results suggest that protective effects of DeCaf on the development of NAFLD are at least in part related to maintaining intestinal barrier function., Graphical abstract fx1, Highlights • decaffeinated coffee protects mice from the development of NAFLD. • decaffeinated coffee attenuated increased translocation of bacterial endotoxins. • decaffeinated coffee prevents diet-induced induction of iNOS in small intestine.